Stabilized organic substances and method of stabilizing same



atented Nov. (8,

FAT 1;

- s'rmrznn oneanro suns'ranons METHODOF s'rnirznro SAME Morris H. Daskais and Ellis K. Fields, Chicago,

1111., assignors to Research Corporation, a corporation. of New York No Drawing. Original application Jan 16, 1943, Serial No. 472,598. Divided and this application February 15, 1943, Serial No. 475,938

11 Claims.

This invention relates to the stabilization of organic substances subject to deterioration by the action of oxygen and, in particular, to the stabilization and preservation of organic substances, especially oxidizable mineral hydrocarbons. wherein the substances contain or are brought in contact with certain metals and their compounds which accelerate the oxidizing action and hasten the deterioration of the organic substances. It also relates to the resulting stabilized products.

This application is a division of our copendingapplication entitled "Organic compounds and method of making same," Serial No. 472,598, filed January 16, 1943. I

I Many organic substances such as gasoline, lubricating oils,-sulfnated and sulfated oils, essential oils, fats, soaps, rubber, photographic developers, silk, wool, cellulose products and the like are subject to oxidation and consequent deterioration. Antioxidants are usually incorporated in these organic substances to retard to a consderable extent the reaction of these substances with oxygen. In the presence of even very minute amounts of certain metals and metallic compounds, especially copper, iron, chromium and lead, and their compounds, which appear to function as oxidation promoters when in contact with organic substances, the eflect of antioxidants is decreased, and may be overcome entirely, so that the organic substances react with oxygen as rapidly as, if not more rapidly than, if an antioxidant were not present.

essential to accomplish this purpose, varying generally from about 0.005% to about /2 of 1%.

. Larger amounts can, of course, be used. The

The use of metal deactivators for the purpose described herein is known: however, most of the compounds-proposed for this purpose have not been particularly efiective. The most efiective ones heretofore proposed, in so far as we are aware, consist oi the products oi condensation oi (a) one molecule of an aliphatic polyamine and two molecules of an ortho hydroxy aromatic alde= hyde or ketone: and (b) one molecule oi a polyaminocompound and at least two molecules of a 1,3 or beta diketone.

We have found that organic substances of the character described are more efiectively'stabilized and preserved by incorporating in these substances a reaction product of an alpha isonitrosocarbonyl compound and an organic polyamine. These reaction products or compounds, while present in the organic substances, suppress and neutralize the pro-oxidant efiect oi-the metals and their compounds on organic substances and enhance the efl ciency oi antl-oxidants-when these latter,

are also present in the organic substances.

Only small ts of these compounds are The compounds usedin accordance with the present invention may be produced by reacting an alpha isonitroso carbonyl compound such as an alpha isonitroso ketone or substituted alpha 'isonitroso ketone with an organic polyamino compound in the proportion of at least two molecules of the former to one of the latter, as fully described in our copending application referred to above. The resulting product is an i'sonitroso ketone-polyamino compound reaction product in which nitrogen atoms are doubly bonded to the carbonyl carbon atoms of the ketone groups and singly bonded to carbon atoms of the hydrocarbon radical. Since the methods of preparin these compounds form no part of the present invention they will not be described herein.

The alpha isonitroso ketone compounds exist in tautomeric form and either or both of these tautomers may be used as a reactant. These tautomers have the following general formulae:

R1 R9 R1 R: (Li or t s t t i itn 3 wherein R1 and Rs represent radicals selected from the group consisting of alkyl, aryl, aralkyl, acyl, carbalkoxy, cyclic or heterocyclic radicals, and

wherein R2 may also be hydrogen, and where the group may occur as LM- of a chain or a cyclic or heterocyclic ring and wherein the carbon atoms of the R1 and Rs groups may be connected directly to each other or through an atom or group of atoms which an. include 0, 0, N, S, etc.

Some examples of such compounds are alpha isonitroso methyl ethyl ketone, isonit'roso acetone, alpha isonitroso camphor, alpha isonitroso aceto-acetic esters, alpha isonltroso acetophenone, alpha isonitroso acetyl acetone, alpha isonitroso cyclohexanone, alpha isonitroso methyl propyl ketone, alpha isonitroso methyl amyl ketone, alpha isonitroso xylyl undecyl ketone, alpha isonitroso acetonaphthone, alpha isonitroso aceto pyridine, etc.

The polyamino compounds referred to are aliphatic-or aromatic. diand higher polyamines, preferably containing at least two primary amino groups attached directly to difierent carbon atoms of the carbon chain. The carbon chain may contain other atoms such as nitrogen, oxygen or sulfur. The amino groups may be attached directlyto different carbon atoms as already pointed out or to different carbon atoms of the carbon chain which are connected by nitrogen, oxygen or sulfur linkages.

Examples of such polyamino compounds are ethylene diamine, 1,2-propylene diamine, 1,3- propylene diamine, 3,4 hexane diamine, diethyle ene triamine, triethylene tetramine, tetraethylene pentamine, ortho phenylene diamine, 1,2-diamino cyclohexane, 1,3-di'amino isopropanol, diamino diethyl ether, diamino diethyl sulfide, etc.

Amongst the alpha isonitroso carbonyl compound-polyamino compound reaction products which we have found to be especially effective as stabilizers and preservers in accordance with the present invention are: I

Di-(isonitroso acetone) ethylene diamine Di-(alpha isonitroso acetoacetic ester) ethylene diamine I Di-(alpha isonitx'oso camphor) ethylene diamine While all of the foregoing compounds are reaction products of two molecules of anisonitroso ketone and one molecule of an vorganic polyamino compound, our invention is not to be construed as limited to the use of such compounds since modified forms of such compounds as well as derivatives thereof may also be used. Thus, modified isonitroso ketone-polyamino reaction products produced by reacting one molecule of an or tho-hydroxy aldehyde or ketone or one molecule of a 1,3-diketone and at least one molecule of an isonitroso ketone with one molecule 01 an organic polyamino compound may be used. The following are examples of such compounds:

N-(alpha isonitroso methyl ethyl ketone)-N'- (ortho-hydroxy acetophenone) -ethylene diamine N- (alpha isonitroso methyl etlwl ketone)-N- (acetyl acetone) -ethylene diamine Derivatives of the isonitroso ketone-polyamino reaction products produced by reacting the reaction product with another organic compound, for example, with an acid chloride or ester such as stearoyl chloride, methyl stearate or ethyl stearate, to obtain an N-disubstituted amide may also 4 be used. The reaction may be represented by the followingequation:

The compounds used in accordance with the present invention were tested on gasoline in accordance with A. S. T. M. method D525-41T for the gum stability of gasoline. The test gasoline contained an antioxidant, but no deactivator and had an induction period of 120 minutes. Just before the test 1 part per million of copper in the form of copper stearate was added to the gasoline, as well as the deactivator to be tested. The results of some tests are shown in Table I.

Table I Induction Deactivstor added 5 mg./60 cc. gasoline period,

minutes None l5 Di-(isonitroso acetone) diethylene triamine Di-(alpha isonitroso methyl ethyl ketone) ethyle diamine 108 Di-(alpha isonitroso methly ethyl ketone) diethylene trlamine Di-(alpha isonitroso acetoacetic ester) ethylene diamine. 90 None 15 oxidation promoter comprising incorporating in said substance a small amount of the condensation reaction product of two molecules of an alpha isonitroso ketone with one molecule of an organic polyprimary amine.

2. The method of increasing the stability of an organic substance subject to deterioration through oxidation while in contact with a metallic oxidation promoter comprising incorporating in said substance a small amount of the condensation reaction product obtained by reacting one molecule of an alpha ison'itroso ketone and one molecule of an ortho-hydrom aromatic carbonylcompound with one molecule of an organic polyprimary amine.

3. An organic substance of improved oxidation stability in contact with metallic oxidation promoters having incorporated therein a small proportion of the condensation reaction product obtained by reacting one molecule of an alpha is'onitroso ketone and one molecule of an ortho-hydroxy aromatic carbonyl compound with one mol ecule of an organic polyprimary amine.

4. An organic substance of improved oxidation stability in contact with metallic oxidation promoters-having incorporated therein a. small pro- '7. An organic substance of improved oxidation stabilityv incontact with metallic oxidation promoters having incorporated therein a small proportion of an alpha isonitroso carbonyl compound-polyamine compound reaction product formed by reacting two molecules of an alpha isonitroso. ketone with one molecule of an organic poly-primary amine.

portion of di-(alpha isonitroso methyl ethyl ketone) ethylene diamine.

5. An organic substance of improved oxidation stability in contact with metallic oxidation promoters having incorporated therein a small proportion of di-(alpha isonitroso methyl ethyl ketone) propylene diamine. v

6. An organic substance of improved oxidation stability in contact with metallic oxidation promoters having incorporated therein a small proportion of di-(alpha isonitroso methyl ethyl ketone) diethylene triamine.

nitroso ketone and one molecule of a carbonyl compound selected from the class consisting of an orthohydroxy aromatic ketone, an ortho-hydroxy a'romatic aldehyde and 1,3-diketone with one molecule of an organic polyprimary amine.

l0. Gasoline containing an antiomdant having incorporated therein a small quantity of di-(alpha isonitroso methyl ethyl ketone) ethylene diamine as a stabilizer against oxidation promoting metals.

11. Gasoline containing an antioxidant having incorporated therein a small quantity .of di- (alpha isonitroso methyl ethyl ketone) diethylene triamine as a stabilizer. 

